Understanding the Reaction Chemistry of 2,2鈥?5鈥?2鈥?Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

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• 作者：Lingzi Sang ; Dallas L. Matz ; Jeanne E. Pemberton
• 刊名：Journal of Physical Chemistry C
• 出版年：2015
• 出版时间：October 29, 2015
• 年：2015
• 卷：119
• 期：43
• 页码：24290-24298
• 全文大小：545K
• ISSN：1932-7455

文摘

The reaction chemistry of vapor-deposited 2,2鈥?5鈥?2鈥?terthiophene (伪-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent 伪-3T and formation of Ag鈥揝 bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with 伪-3T initiated by metal-to-伪-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: one leading to 伪-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-伪-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.